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    A Combined Computational–Experimental Study of the Kinetics of Intramolecular Diels–AlderReactions in a Series of 1,3,8-Nonatrienes

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    Authors
    Lording, W.
    Payne, Alan
    Cayzer, T.
    Sherburn, M.
    Paddon-Row, M.
    Date
    2014
    Type
    Journal Article
    
    Metadata
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    Citation
    Lording, W. and Payne, A. and Cayzer, T. and Sherburn, M. and Paddon-Row, M. 2014. A Combined Computational–Experimental Study of the Kinetics of Intramolecular Diels–AlderReactions in a Series of 1,3,8-Nonatrienes. Australian Journal of Chemistry. 68 (2): pp. 230-240.
    Source Title
    Australian Journal of Chemistry
    DOI
    10.1071/CH14430
    ISSN
    0004-9425
    URI
    http://hdl.handle.net/20.500.11937/28005
    Collection
    • Curtin Research Publications
    Abstract

    Activation enthalpies for a series of five 1,3,8-nonatriene intramolecular Diels–Alder (IMDA) reactions involving substrates 1–5 have been determined experimentally and Singleton’s natural abundance method has been employed to determine kinetic isotope effects in the IMDA reaction of fumarate 3. The activation enthalpies for the IMDA reactions of the systems possessing a –CH2OCH2– diene/dienophile tether are significantly smaller than their counterparts possessingthe –CH2OC(¼O)– tether. The experimental activation enthalpies have been used to benchmark computed values from four model chemistries, namely two density functional theory functionals, B3LYP and M06-2X, and two generally very accurate composite ab initio wave function methods, CBS-QB3 and G4(MP2). G4(MP2) outperformed the computationally more expensive CBS-QB3 method, but the vastly cheaper M06-2X/6-31G(d)//B3LYP/6-31G(d) method was sufficiently accurate to be the recommended method of choice for calculating activation parameters. Experimental 2H kinetic isotope effects for the IMDA reaction of fumarate 3 confirmed the computational predictions that this Diels–Alder reaction is concerted but asynchronous.

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